The Internet of Vehicles (IoV) enables vehicular data services and applications through vehicle-to-everything (V2X) communications. One of the key services provided by IoV is popular content distribution (PCD), which aims to quickly deliver popular content that most vehicles request. However, it is challenging for vehicles to receive the complete popular content from roadside units (RSUs) due to their mobility and the RSUs’ constrained coverage. The collaboration of vehicles via vehicle-to-vehicle (V2V) communications is an effective solution to assist more vehicles to obtain the entire popular content at a lower time cost. To this end, we propose a multi-agent deep reinforcement learning (MADRL)-based popular content distribution scheme in vehicular networks, where each vehicle deploys an MADRL agent that learns to choose the appropriate data transmission policy. To reduce the complexity of the MADRL-based algorithm, a vehicle clustering algorithm based on spectral clustering is provided to divide all vehicles in the V2V phase into groups, so that only vehicles within the same group exchange data. Then the multi-agent proximal policy optimization (MAPPO) algorithm is used to train the agent. We introduce the self-attention mechanism when constructing the neural network for the MADRL to help the agent accurately represent the environment and make decisions. Furthermore, the invalid action masking technique is utilized to prevent the agent from taking invalid actions, accelerating the training process of the agent. Finally, experimental results are shown and a comprehensive comparison is provided, which demonstrates that our MADRL-PCD scheme outperforms both the coalition game-based scheme and the greedy strategy-based scheme, achieving a higher PCD efficiency and a lower transmission delay.